Water-soluble,yellow mono-azo dyes with active methylene coupler

ABSTRACT

AZO DYES OF THE FORMULA   (2,4-BIS(R-O-),5-X-PHEN-1-YL)-NH-CO-CH(-CO-CH3)-N=N-   ME-O3S-S-(CH2)2-NH-SO2-BENZENE   IN WHICH R STANDS FOR METHYL OR ETHYL, X STANDS FOR HYDROGEN OR CHLORINE, AND ME REPRESENTS AN ALKALI METAL OR AMMONIUM, ARE PREPARED BY COMBINING DIAZOTIZED 2(4&#39;&#39;-AMINO-BENZENESULFONYLAMINO)-ETHYL-THIOSULFURIC ACID WITH A COUPLING COMPONENT OF THE FORMULA   1-(CH3-CO-CH2-CO-NH-),2,4-BIS(R-O-),5-X-BENZENE   IN WHICH R STANDS FOR METHYL OR ETHYL AND X STAND FOR HYDROGEN OR CHLORINE, AT A TEMPERATURE BETWEEN 0*C. AND 20*C. AND A PH BETWEEN 2 AND 6, WHICH AZO DYES ARE READILY SOLUBLE IN WATER AND HAVE GOOD TO EXCELLENT FASTNESS WHEN APPLIED TO NATIVE OR REGENERATED CELLULOSE, CELLULOSE ACETATE, WOOL, SILK, LEATHER AND SYNTHETIC MATERIALS SUCH AS POLYSTER AND ESPECIALLY POLYAMIDE FIBERS.

United States Patent 3,577,405 WATER-SOLUBLE, YELLOW MONO-AZO DYES WITHACTIVE METHYLENE COUPLER Hermann Holimann, East Greenwich, and HelmutSchmidt, Warwick, R.I., assignors to American Hoechst Corporation, NewYork, N.Y. No Drawing. Filed May 8, 1968, Ser. No. 727,715 Int. Cl. C07c107/04; C09b 29/32 US. Cl. 260-193 8 Claims ABSTRACT OF THE DISCLOSUREAzo dyes of the formula in which R stands for methyl or ethyl, X standsfor hydrogen or chlorine, and Me represents an alkali metal or ammonium,are prepared by combining diazotized 2- (4amino-benzenesulfonylamino)-ethyl-thiosulfuric acid with a couplingcomponent of the formula in which R stands for methyl or ethyl and Xstands for hydrogen or chlorine, at a temperature between 0 C. and 20 C.and a pH between 2 and 6, which azo dyes are readily soluble in waterand have good to excellent fastness when applied to native orregenerated cellulose, cellulose acetate, wool, silk, leather andsynthetic materials such as polyester and especially polyamide fibers.

The present invention relates to new water-soluble, yellow azo dyestuffscontaining one thiosulfuric acid group, and to a process for theirpreparation; more particularly it relates to dyestuffs of the formula inwhich R stands for methyl or ethyl, X stands for hydrogen or chlorine,and Me represents an alkali metal or ammonium.

3,577,405 Patented May 4, 1971 "ice It has been known that water-solubleazo dyes containing thiosulfuric acid groups can be obtained by the reaction of diazotized aromatic amines containing thiosulfuric acid groupswith compounds capable of being coupled in an acid, neutral or alkalinesolution; more particularly it has been known, from US. Patent3,098,064, that water-soluble azo dyes of the formula in which one X oneach of the benzene rings stands for hydrogen and the other X stands forhydrogen, methyl methoxy or chlorine, one Y stands for hydrogen ormethoxy and the other Y stands for hydrogen, methyl, methoxy orchlorine, and Me represents an alkali metal or ammonium, can be preparedby the reaction of diazotized aromatic amines containing a thiosulfuricacid group such as 2 (3-amino-benzenesulfonylamino)-ethyl-thiosulfuricacid, 2 (3-amino-6'-chlorobenzenesulfonylamino)-ethylthiosulfuric acid,2-(3-amino-6'-methyl-benzenesulfonylamino)-ethyl-thiosulfuric acid, 2(3-amino-4'-methoxybenzenesulfonylamino)-ethyl-thiosulfuric acid withdi- (acetoacetylamino)-benzenes such as1,4-di-(acetoacetylamino)-benzene, 1,4di-(acetoacetylamino)-2-chlorobenzene, 1,4di-(acetoacetylamino)-2-chloro-5-methoxybenzene,2,5-di-(acetoacetylamino)-toluene, 2,5-di-(acetoacetylamino)-anisol or2,5-di-(acetoacetylamino)-hydroquinone-dimethylether.

It has now been found that water-soluble, yellow azo dyestuffs of theformula in which R stands for methyl or ethyl, X stands for hydrogen orchlorine, and Me is an alkali metal or ammonium, can be preparedadvantageously by the reaction of diazotized 2(4-amino-benzenesulfonylamino)-ethylthiosulfuric acid with anacetoacetylamino-2,4-dialkoxybenzene such asacetoacetylamino-2,4-dimethoxy-benzene, acetoacetylamino 2,4diethoxy-benzene or acetoacetylamino-2,4-dimethoxy-5-chloro-benzene.

More specifically, the coupling reaction is carried out Thecorresponding 2,4-dimethoxy-5-chloroand 2,4- by the addition of asolution of the coupling component diethoxy-benzene acetoacetylamino azodyes are obtamin aqueous alkali to an aqueous suspension of the diazoable by the same procedure as descr bed in the examcompound at atemperature between C. and 20 C. and ple by using acetoacetylamlno 2,4dimethoxy--chloroa pH between 2 and 7. When the coupling reaction is 5benzene and acetoacetylamino-2,4-d1ethoxy-benzene, refinished, the pH ofthe mixture is adjusted to between spectively, as coupling components. 7and 9 and the dyestufi is filtered, if necessary after We claim: theaddition of salt, 1. A water-soluble, yellow azo dyestufl of the formulaDyes obtainable according to the present invention are OR easily solublein water, the solutions having very little I tendency to form gels.

They can be applied to native or regenerated cellulose, Q I celluloseacetate, wool, silk or leather as well as to syn- X T thetic materialslike polyester fibers. They are especially valuable for dyeing polyamidefibers due to the high afiinity they have for this material and theexcellent fastness properties these dyeings exhibit. -S 0zNHCHzOHz-S s03MB EXAMPLE in which R stands for methyl or ethyl, X stands for hy- Asolution of 22 parts of sodium nitrite in 67 parts of drogen orchlorine, and Me represents an alkali metal water is added at 0 C-2 C.within one hour to an agior ammonium.

tated mixture of 100 parts of 2-(4-amino-benzene-sulfo- 2. A dyestutf ofthe formula (3H nylamino)-ethyl-thiosulfuric acid, 230 parts of water,240 wherein Me is an alkali metal or ammonium ion. parts of ice and 44parts of concentrated hydrochloric 3. A dyestutf of the formula Ha acid.The mixture is agitated for one hour, whereafter exwherein Me is analkali metal or ammonium ion. cess nitrite is destroyed by the additionof 2-3 parts of 4. A dyestuff of the formula (l) CzH5 en, sulfamic acid.After adjustment of the pH to 4-5 by the wherein Me is an alkali metalor ammonium ion. addition of 60 parts of sodium acetate and thenecessary 5. A dyestufi according to claim 1 wherein Me is soamount ofsodium bicarbonate, a solution of 76 parts of dium.acetoacetylamino-2,4-dimethoxy-benzene in 250 parts of 6. A dyestuifaccording to claim 2 wherein Me is sowater containing 16 parts of sodiumhydroxide is added dium. at 0 C.5 C. over a period of 1-2 hours. The pHof 7. A dyestufi according to claim 3 wherein Me is sothe mixture isthen adjusted to 8 by the addition of sodium. dium hydroxide and thedyestuif is filtered and dried. 8. A dyestuif according to claim 4wherein Me is so- Yield: 200 parts of a yellow powder which is solublein dium. water.

References Cited A solution of 2.0 g. of the above described dyestutf,UNITED STATES PATENTS 1.25 ml. of 25% aqueous ammonia and 4.00 g.ammonium acetate in 4000 ml. of water is heated to 30 C. 3,098,0647/1963 sc,hultheis at 260-176 100 g. of nylon yarn are dyed in thissolution for 10 min- 3,132,134 5/1964 et a1 260 193 utes. Thetemperature is then raised to 70 C. and kept 3197456 7/1965 Kuhne 260193X there for 30 minutes. After addition of 0.5 ml. of 56% acetic acid,the temperature is kept at C. for another CHARLES PARKER Primary Exammer15 minutes. The material is then rinsed, soaped at 70 C., C. F. WARREN,Assistant Examiner rinsed again and dried. The procedure results in abrilliant yellow dyeing of greenish cast with excellent fastness tolight exposure and excellent wet fastness characteristics. 7 812, 41,50, 51.

